US4301236A - Photographic bleach solutions - Google Patents

Photographic bleach solutions Download PDF

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US4301236A
US4301236A US06/114,456 US11445680A US4301236A US 4301236 A US4301236 A US 4301236A US 11445680 A US11445680 A US 11445680A US 4301236 A US4301236 A US 4301236A
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acid
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Yoshio Idota
Minoru Yamada
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/144—Hydrogen peroxide treatment

Definitions

  • This invention relates to a photographic processing for silver halide color photographic materials and, more particularly, to a photographic bleach solution for silver halide color photographic materials having a sufficient bleaching activity and capable of forming color images having good quality.
  • a color photographic material (the silver halide photographic emulsions thereof may have been fogged beforehand) is developed in an ordinary manner, after being imagewise exposed using a developer containing an aromatic primary amine color developing agent in the presence of dye forming couplers to provide color images and developed silver formed simultaneously with the formation of the color images is re-halogenated by bleaching and is removed by fixing (or blixing) together with undeveloped silver halides.
  • a ferricyanide, ferric chloride, aminopolycarboxylic acid ferric complex salt, etc. have mainly been used as a bleaching agent.
  • a ferrycyanide and ferric chloride are good bleaching agents in the points that they have a sufficiently high bleaching speed (oxidizing speed) and developed silver is sufficiently oxidized in a definite period of time.
  • oxidizing speed oxidizing speed
  • a treatment must be applied to make the waste bleach solution completely nontoxic.
  • a bleach solution using ferric chloride as bleaching agent has a fault that parts of a processor containing the bleach solution are liable to be corroded owing to the very low pH and very large oxidative power as well as has a fault that in the wash step after bleach processing, iron hydroxide deposits in silver halide emulsion layers to cause so-called stains. Consequently, a cleaning step by an organic chelating agent must be applied after bleaching, which conflicts with the purposes to process quickly and save labour, and also the use of such a bleach solution is undesirable in terms of environmental problems since there is a danger of generating a hydrogen chloride gas.
  • a metal complex of an organic acid such as a metal complex salt of aminopolycarboxylic acid gives less environmetal pollution as compared with a ferricyanide or ferric chloride and hence such a complex salt has frequently been used recently as bleaching agent.
  • an organic metal complex as bleaching agent has generally a relatively low oxidative power and is also insufficient in bleaching power
  • a bleaching solution using the complex salt as bleaching agent is used for bleaching, for example, a desired object may be attained to some extent using low speed silver halide color photographic materials mainly composed of silver chlorobromide emulsions, but when the bleach solution is used for bleaching high speed silver halide color photographic materials which are mainly composed of silver iodochlorobromide emulsions or silver iodobromide emulsions and have been color-sensitized, (in particular silver halide color photographic materials using high silver content silver halide emulsions) the removal of silver becomes poor due to the insufficient bleaching action and so-called poor recoloring occurs (i.e., the dyes formed by the oxidative coupling of the oxidation product of a color developing agent and couplers remain as leuco dyes which are reaction intermediates).
  • high silver content silver halide emulsions refers to silver halide emulsions having no more than 30-40 mg/100 cm 2 of the total silver amount in blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers.
  • the use of hydrogen peroxide is accompanied by a fault that the layers of photographic materials are broken during processing.
  • a metal such as stainless steel, etc., is used for automatic processors and in case of using such a bleach solution, there is a fault that hydrogen peroxide contained in the bleach solution causes self-decomposition by the catalytic action of the metal to reduce the bleaching power of the bleach solution.
  • hydrogen peroxide is a strong oxidizing agent but when hydrogen peroxide is simply used as a bleaching agent, it is impossible to practically use hydrogen peroxide for bleaching silver in color photographic materials.
  • a first object of this invention is, therefore, to provide an effective bleach solution for silver halide color photographic materials containing hydrogen peroxide as the main bleaching component.
  • a second object of this invention is to provide a bleach solution of silver halide color photographic materials causing no environmental pollution, having excellent storage stability, and showing a high bleaching speed.
  • a third object of this invention is to provide a processing process for silver halide color photographic materials without so-called poor recoloring phenomenon that the dyes formed by oxidative coupling remain in the state of leuco dyes after bleach step.
  • a fourth object of this invention is to provide a process for processing silver halide color photographic materials which always maintains a stable bleaching power.
  • a bleach solution comprising hydrogen peroxide (or a compound releasing hydrogen peroxide or a mixture of hydrogen peroxide and a compound releasing hydrogen peroxide), an organic acid metal complex salt, and at least one substituted or unsubstituted aromatic sulfonic acids (including salts thereof and the acid may have two or more sulfon groups).
  • the organic acid metal complex salts used in this invention are compounds having the ability to convert metallic silver formed by development into silver halide by oxidizing it and simultaneously converting leuco dyes into dyes, and they have a structure formed by chelating an aminopolycarboxylic acid, an organic phosphonic acid, or polycarboxylic acid such as citric acid, oxalic acid, etc., with a high valent metal ion such as iron (III) ion, cobalt(III) ion, copper(II) ion, etc.
  • Chelating agents used for forming the complex salts used in this invention are the polycarboxylic acids represented by following formula I:
  • R 1 represents a single bond, an unsubstituted or substituted alkylene group having 1 to 6 carbon atoms wherein the substituent is a hydroxy group and/or a carboxy group, a --(CH 2 ) m --O--(CH 2 ) n -- group wherein m and n are integers and m+n is 2 to 6, a --(CH 2 ) m' --S--(CH 2 ) n' -- group wherein m' and n' are integers and m'+n' is 2 to 6, or an alkenylene group having 2 to 6 carbon atoms; l represents an integer of 2 to 3; and when R 1 is a single bond, l is 2.
  • Chelating agents used for forming the complex salts used in this invention are the aminopolycarboxylic acids represented by following formula II: ##STR1## wherein R 2 , R 3 , R 4 and R 5 each represents a carboxyalkyl group wherein the alkyl moiety has 1 to 2 carbon atoms, a hydroxyalkyl group having 1 to 2 carbon atoms and/or a hydrogen atom; p represents zero or an integer of 1 to 3; L represents an alkylene group having 2 to 4 carbon atoms, a --CH 2 ) x [O--CH 2 ) y ] z group wherein x is an integer of 2 to 4, y is an integer of 2 to 4 and z is an integer of 1 to 3, a 6-membered cyclic alkylene group, or an arylene group (e.g., phenylene); and the aminopolycarboxylic acid of the formula (II) has at least 1 carboxy group.
  • aminopolycarboxylic acids of the formula (II) or the salts thereof are as follows:
  • Phenylenediaminetetraacetic acid Phenylenediaminetetraacetic acid.
  • Chelating agents used for forming the complex salts used in this invention are the organic phosphonic acids represented by following formulae III-a or III-b:
  • R 6 represents a substituted or unsubstituted alkyl or alkylene group having 1 to 4 carbon atoms wherein the substituent is a hydroxy group and/or a carboxy group, or a substituted or unsubstituted diaminoalkylene group having 2 to 16carbon atoms wherein the substituent is a hydroxy group;
  • L represents an alkylene group having 1 to 2 carbon atoms; and
  • q represents an integer of 1 to 5.
  • Preferred examples of the chelating agent are an ethylenediaminetetraacetic acid and a salt thereof and an ethylenediamine-N-( ⁇ -oxyethyl)-N,N'-N'-triacetic acid and a salt thereof.
  • ferric ions are preferred and in this case, the proportion of the ferric ions is 0.0001 to 2 moles, preferably 0.01 to 0.2 mole per liter of bleach solution.
  • perboric acid (or salts thereof), and percarbonic acid (or salts thereof) are preferred.
  • Urea-hydrogen peroxide compound and peracetic acid are also useful.
  • the proportion of hydrogen peroxide or the compound releasing hydrogen peroxide is about 0.1 to 10 moles, preferably 0.1 to 2 moles per liter of bleach solution. In this invention, a preferred effect is achieved if the mole number of hydrogen peroxide (or percursor) per liter of the bleach solution is larger than that of the ferric ion and further it is more preferred that the mole number of the hydrogen peroxide is twice as large as the ferric ion.
  • substituted or unsubstituted aromatic sulfonic acids (or salts thereof) or substituted or unsubstituted aromatic polyvalent sulfonic acids (or salts thereof) used in this invention can be represented by following formula IV:
  • M represents a hydrogen atom, an alkali metal atom (e.g., sodium or potassium), or an ammonium group
  • r represents an integer of 1 to 5
  • Q represents an aromatic hydrocarbon group or an aromatic heterocyclic group including at least one nitrogen atom or sulfur atom. These aromatic groups may have one or more substituents.
  • substituents are aliphatic groups or aromatic hydrocarbon groups (each of which may be substituted by, e.g., a carboxyl group, a hydroxy group, an amino group, a nitro group, a nitroso group, or a halogen atom), a carboxy group, a hydroxy group, an amino group, a nitro group, a nitroso group, and a halogen atom.
  • a proper addition amount of the compound shown by general formula IV is about 5 ⁇ 10 -5 to 0.3 mole, prefrably about 10 -3 to 0. 1mole per liter of bleach solution.
  • polymer it means a mole number of sulfon groups.
  • This invention is distinguished from conventional techniques by the following reasons.
  • Hydrogen peroxide itself has very low rate for oxidizing silver but when a very small amount of a ferric ion which oxidizes silver very slowly is added to hydrogen peroxide, the rate of bleaching silver by the system becomes very high. Thus, it is expected that hydrogen peroxide is decomposed by the catalytic action of the iron ions to generate an oxidative power (this is well known decomposition reaction of a Fenton reagent).
  • Japanese patent application (OPI) No. 102296/78 discloses that a condensation product of naphthalenesulfonic acid and formalin controls the decomposition of hydrogen peroxide in the presence of iron ions.
  • the bleaching rate is not reduced by the addition of a compound having a sulfon group and further the reduction in oxidative power during storage as occurs in the above-described co-existing system of ferric ions and hydrogen peroxide can be prevented, and hence the invention provides an effect which is unusual by comparison to the conventional techniques.
  • a ferric ion exists at the abovedescribed concentration and the existence of the ion has the effect of increasing the storage stability of the bleach solution containing hydrogen peroxide as the main component.
  • the bleach solution of this invention has the following effect. That is, it is known that hydrogen peroxide causes self-decomposition by the catalytic action of a metal such as stainless steel but the bleach solution of this invention can restrain the self-decomposition of hydrogen peroxide and hence stainless steel, titanium alloys, etc., can be used for automatic precessors in this invention.
  • the bleach solutions used in this invention may further contain various additives together with the abovedescribed compounds.
  • Preferred additives used in this invention for accelerating bleaching are halides such as alkali halides and ammonium halides, for example, potassium bromide, sodium bromide, ammonium bromide, sodium chloride, etc.
  • the addition amount of the additive is about 0.01 to 5 moles, preferably about 0.2 to 2 moles per liter of the bleach solution.
  • an aliphatic carboxylic acid such as, for example, acetic acid, acetates, propionic acid, propionates, succinic acid, succinates, malonic acid, malonates, citric acid, citrates, 2,2-diphosphonoethanol or the salts thereof, and 2-phosphono-1,2,4-tricarboxylic acid or the salts thereof
  • the addition amount of it is about 0.01 to 5 moles, preferably about 0.1 to 1 mole per liter of the bleach solution.
  • additives which are conventionally used in bleach solutions, for example, a pH buffer such as a borate, an acetate, a phosphate, etc.; a pH adjusting agent such as sodium hydroxide, ammonia water, etc.; a corrosion inhibitor such as ammonium nitrate, etc.; a swelling preventing agent such as ammonium sulfate, a surface active agent (e.g., polyethylene oxide, etc.), etc., can be properly added.
  • a pH buffer such as a borate, an acetate, a phosphate, etc.
  • a pH adjusting agent such as sodium hydroxide, ammonia water, etc.
  • a corrosion inhibitor such as ammonium nitrate, etc.
  • a swelling preventing agent such as ammonium sulfate, a surface active agent (e.g., polyethylene oxide, etc.), etc.
  • the pH of the bleach solution used in this invention is about 1 to 10, preferably about 3 to 8.
  • the bleaching temperature is typically from 20° to 60° C.
  • a substituted alkylthiol compound or a precursor may be used as a bleach accelerator in a bath used prior to the bleach bath.
  • Typical examples of the substituted alkylthiol compounds or the precursors thereof are described in U.S. Pat. No. 3,893,858; Research Disclosure, 15704 (1977, May); and Japanese patent application (OPI) Nos. 20832/77; 32736/78; 94927/78; 95630/78 and 95631/78.
  • R represnts an alkyl group having 1 to 10 carbon atoms, which may have one or more substituents and may be branched; at least one of the substituents for group R being a hydroxy group, a primary, a secondary, a tertiary amino group, a carboxy group, a sulfon group, a piperidino group, a pyrrolyl group, a morpholino group, an imidazole group, or a benzotriazole group; and Y represents a hydrogen atom or an amidino group.
  • These compounds may form salts such as chlorides.
  • the above-described compounds are typical examples and the invention is not limited to these compounds.
  • the addition amount of this additive is about 1 ⁇ 10 -5 to 1 mole/liter, preferably about 1 ⁇ 10 -3 to 1 ⁇ 10 -1 mole/liter.
  • the processing baths containing these compounds include a processing bath used after the color development bath and prior to the bleach bath. For example, there is a stop bath, and a stop-fix bath.
  • the bleaching period can be greatly shortened.
  • the bleach solution of this invention used can be easily reproduced for reuse by adding hydrogen peroxide thereto.
  • This invention can be applied to the processing of whole color photographic materials using silver halide emulsions, such as color papers, color negative films, color reversal films, color positive films, etc., but when the bleach solution of this invention is used for processing color photographic materials using high silver content silver halide emulsions having a total silver content in silver halide emulsion layers of 30 mg/100 cm 2 or more, the effect of this invention is large and when the invention is used for the processing of color photographic materials having a total silver amount of 40 mg or more per 100 cm 2 , the invention is particularly useful.
  • processings for imagewise exposed color negative films, color positive films, color papers, etc. are fundamentally composed of the following steps:
  • a pre-bath, a hardening bath, etc. may be employed before the color development and also a stabilization or a wash after bleach may be omitted.
  • processings for color reversal films are fundamentally composed of the following steps:
  • a pre-bath In processings (5) and (6), a pre-bath, a pre-hardening bath, a neutralization bath, etc., may be employed. Also, a stabilization or a wash after bleach may be omitted. Furthermore, the fogging bath may be replaced with reexposure and also by adding a fogging agent to the color developer, the fogging bath may be omitted.
  • the color developer used in this invention has a composition for ordinary color developer containing an aromatic primary amine developing agent and preferred examples of the aromatic primary amine color developing agent are such p-phenylenediamine derivatives as N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5-(N-ethyl-N-laurylamino)toluene, 4-[N-ethyl-N-( ⁇ -hydroxyethyl)amino]aniline, 2-methyl-4-[N-ethyl-N-( ⁇ -hydroxyethyl)-amino]aniline, N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline described in U.S.
  • the color developer may further contain other known components used in ordinary color developers.
  • sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium or potassium tertiary phosphate, potassium metaborate, borax, etc. may be used solely or as a combination thereof as an alkalifying agent or a buffer.
  • various salts such as di-sodium or di-potassium hydrogenphosphate, potassium or sodium dihydrogenphosphate, sodium or potassium hydrogencarbonate, boric acid, an alkali nitrate, an alkali sulfate, etc., can be also used together with the above-described additive for giving buffer action, for the convenience of preparing color developers, or for increasing the ionic strength.
  • the color developer may contain, if necessary, a development accelerator.
  • a development accelerator for example, there are various pyridinium compounds and other cationic compounds described in U.S. Pat. No. 2,648,604; Japanese Patent Publication 9503/69 and U.S. Pat. No. 3,671,247; cationic dyes such as phenosafranine; neutral salts such as thallium nitrate and potassium nitrate; nonionic compounds such as polythioethers, polyethylene glycol and the derivatives thereof described in Japanese patent publication No. 9504/69; and U.S. Pat. Nos.
  • sulfites such as, for example, sodium sulfite, potassium sulfite, potassium hydrogensulfite, and sodium hydrogensulfite as well as hydroxylamine, ascorbic acid, pentose, hexose, etc., usually used as preservatives in photographic field may be added to the color developers used in this invention.
  • the color developers used in this invention may further contain, if necessary, any desired antifoggant.
  • antifoggants used in this invention there are alkali metal halides such as potassium bromide, sodium bromide, potassium iodide, etc., and organic antifoggants.
  • organic antifoggants are nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, etc.; mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, etc.; and mercapto-substituted aromatic compounds such as thiosalycilic acid, etc.
  • Preferred examples of organic antifoggants are nitrogen-containing heterocyclic compounds, in particular nitrogen-containing heterocyclic compounds which have not been substituted by mercapto group.
  • the proportion of the antifoggant is about 1 mg to 5 g, preferably 5 mg to 1 g per liter of the color developer.
  • polyphosphoric acid compounds exemplified by sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, potassium hexametaphosphate, potassium tetrapolyphosphate, potassium tripolyphosphate, etc.; or aminopolycarboxylic acids exemplified by phosphonocarboxylic acid, ⁇ -aminoacid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, etc., may be used as a water softener for the color developers.
  • the addition amount of the material depends upon the hardness of water to be used but is usually about 0.5 to 1 g/liter.
  • calcium or magnesium covering agents can be used in the photographic processing solutions in this invention. They are described in detail in, for example, J. Williams, Belgische Chemische Industrie, Vol. 21, page 325 (1956) and ibid., Vol. 23, page 1105 (1958).
  • fogging agents used in this invention there are alkali metal borohydrides (e.g., sodium borohydride), amineboranes (e.g., t-butylamineborane), tin-aminopolycarboxylic acid complex salts, tin-pyrophosphoric acid complex salts, tin-tetrapolyphosphoric acid complex salts, tin-hexametaphosphoric acid complex salts, ethylenediamine, etc. Also, the compounds described in Japanese patent publication 38816/72 are useful for the fogging agent.
  • alkali metal borohydrides e.g., sodium borohydride
  • amineboranes e.g., t-butylamineborane
  • tin-aminopolycarboxylic acid complex salts e.g., tin-pyrophosphoric acid complex salts
  • tin-tetrapolyphosphoric acid complex salts tin-hexametaphosphoric acid
  • compensation developing agents used in this invention there are p-aminophenyl, N-benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone, etc.
  • Other examples of the compensation developing agent used advantageously in this invention are described in, for example, Japanese patent publications Nos. 41475/70 and 19037/71.
  • the pH of the color developer used in this invention is about 7 to 14, preferably about 8 to 13.
  • the processing process of this invention can be applied not only to a color photographic system wherein dye forming couplers are incorporated in color photographic materials as described in, for example, U.S. Pat. Nos. 2,322,027; 2,376,679 and 2,801,171 but also to a color photographic system wherein couplers are incorporated in color developers as described in, for example, U.S. Pat. Nos. 2,252,718; 2,590,970 and 2,592,243.
  • the former system is mainly performed.
  • dye forming couplers are incorporated in color photographic materials
  • multilayer color photographic materials are generally used and in this case it is preferred that the couplers remain in definite emulsion layers and do not diffuse into other emulsion layers during the production steps thereof, preservation, and processing steps for them.
  • a fix solution having a composition usually used for the purpose can be used in this invention.
  • a fixing agent there are thiosulfates, thiocyanates, thioureas, thioglycols, water-soluble organic diols containing sulfur or oxygen in the molecule (e.g., 3,6-dithia-1,8-octyldiol), etc.
  • the fixing solution may further contain a stabilizer such as a sulfite (e.g., sodium sulfite), etc., and a pH buffering salt or a swelling inhibiting salt (e.g., a hardening agent such as potassium alum) and when a thiosulfate is used as the fixing agent, the use of the aforesaid stabilizer is particularly preferred.
  • a stabilizer such as a sulfite (e.g., sodium sulfite), etc.
  • a pH buffering salt or a swelling inhibiting salt e.g., a hardening agent such as potassium alum
  • the black and white developer used in a silver dye bleaching process or a reversal color photographic process in this invention may contain a developing agent generally used in black and white developers.
  • a developing agent e.g., a dihydroxybenzene (e.g., hydroquinone, sodium hydroquinonemonosulfonate, etc.), a 3-pyrazolidone (e.g., 1-phenyl-3-pyrazolidone, etc.), an aminophenol (e.g., N-methyl-p-aminophenol, etc.), ascorbic acid, etc., may be used solely or as a combination thereof.
  • the developer may further contain a preservative, an alkalifying agent, a pH buffer, an antifoggant, etc., and also, if necessary, it may further contain a dissolution aid, a toning agent, a development accelerator, a surface active agent, a defoaming agent, a water softener, a hardening agent, a tackifier, etc., well-known about the detail of them in the field of the art.
  • the photographic silver halide emulsion layers of the color photographic materials used in this invention may contain color image-forming couplers, that is, the compounds forming dyes by the reaction with the oxidation product of an aromatic amine (usually primary amine) developing agent (hereinafter, referred to as simply couplers).
  • the couplers are preferably non-diffusible ones having a hydrophobic group called as a ballast group in the molecule.
  • the couplers may be 4-equivalent ones or two-equivalent ones for silver ion.
  • the silver halide emulsion layers may further contain colored couplers having an effect of color correction or couplers releasing a development inhibitor with the progress of development (i.e., so-called DIR couplers). Still further, the couplers may be couplers providing colorless products by the coupling reaction thereof.
  • yellow coupling coupler known open chain ketomethylene couplers can be used.
  • benzoylacetanilide series compounds and pivaloylacetanilide series compounds are advantageously used in this invention.
  • Practical examples of the yellow coupling couplers are described in U.S. Pat. Nos. 2,875,057; 3,265,506; 3,408,194; 3,551,155; 3,582,322; 3,725,072; and 3,891,445; West German patent No. 1,547,868; West German patent publications (OLS) Nos. 2,219,917; 2,261,361 and 2,414,006; U.K. Pat. No. 1,425,020; Japanese patent publication No.
  • magenta coupling couplers used in this invention there are pyrazolone series compounds, indazolone series compounds, and cyanoacetyl series compounds but in particular, pyrazolone series compounds are more useful.
  • Practical examples of the magenta coupling couplers are described in U.S. Pat. Nos. 2,600,788; 2,983,608; 3,062,653; 3,127,269; 3,311,476; 3,419,391; 3,519;429; 3,558,319; 3,582,322; 3,615,506; 3,834,908; and 3,891,445; West German Pat. No. 1,810,464; West German patent application (OLS) Nos.
  • cyan coupling couplers used in this invention there are phenol series compounds, naphthol series compounds, etc. Practical examples of them are described in U.S. Pat. Nos. 2,369,929; 2,434,272; 2,474,293; 2,521,908; 2,895,826; 3,034,892; 3,311,476; 3,458,315; 3,476,563; 3,583,971; 3,591,383; 3,767,411 and 4,004,929; West German patent application (OLS) Nos. 2,414,830 and 2,454,329; and Japanese patent application (OPI) Nos. 59838/73; 26034/76; 5055/73; 146828/76; 69624/77 and 90932/77.
  • DIR couplers used in this invention are described in, for example, U.S. Pat. Nos. 3,227,554; 3,617,291; 3,701,783; 3,790,384 and 3,632,345; West German patent application (OLS) Nos. 2,414,006; 2,454,301 and 2,454,329; U. K. Pat. Nos. 953,454; Japanese patent application (OPI) Nos. 69624/77; 122335/74 and 69624/77 and Japanese patent publication No. 16141/76.
  • the color photographic materials used in this invention may further contain compounds releasing a development inhibitor at development and examples of these compounds are described in, for example, U.S. Pat. Nos. 3,297,445 and 3,379,529; West German patent application (OLS) No. 2,417,914; and Japanese patent application (OPI) Nos. 15271/77 and 9116/78.
  • the couplers described above may be incorporated as a combination of two or more couplers in the same silver halide emulsion layer of a color photographic material or the same coupler may be incorporated in two or more silver halide emulsion layers of a color photographic material.
  • couplers are dispersed in silver halide photographic emulsions together with a solvent having a proper polarity.
  • solvents for the purpose are tri-o-cresyl phosphate, trihexyl phosphate, dioctylbutyl phthalate, dibutyl phthalate, diethyllaurylamide, 2,4-diallyl phenol, octyl benzoate, etc.
  • Typical examples of the color image forming materials used in the color photographic materials for silver dye bleach process processed according to this invention are, for example, azo dyes.
  • the color photographic material processed according to this invention has at least one silver halide emulsion layer on a support and usually has a red sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer and a blue sensitive silver halide emulsion layer on a support. More practically, the color photographic material used in this invention has usually at least a red sensitive silver halide emulsion layer containing a cyan image forming coupler, at least a green sensitive silver halide emulsion layer containing a magenta image forming coupler, and at least a blue sensitive silver halide emulsion layer containing a yellow image forming coupler.
  • Such a color photographic element may further include non-photosensitive photographic layers (e.g., antihalation layer, interlayer for color mixing prevention, etc., yellow filter layer, protective layer, etc.). Also, there is no particular restriction about the order of the red sensitive emulsion layer, the green sensitive emulsion layer and the blue sensitive emulsion layer described above.
  • the silver halide photographic emulsions used in this invention may be surface latent image type emulsions or inside latent image type emulsions which are prepared by known processes.
  • the bleach solution can be easily regenerated for reuse.
  • a color reversal photographic material was prepared by coating a triacetate film successively with the following layers in order.
  • the coating composition for the emulsion layer was prepared by mixing a red sensitive silver iodobromide emulsion (silver iodide: 7 mole percent) and a cyan coupler emulsion (containing 1-hydroxy-4-chloro-2-n-dodecylnaphthamide as a cyan coupler and dibutyl phthalate as a coupler solvent) in such a manner that the silver/coupler mole ratio became 8.0.
  • the coverage of silver was 1.5 g/m 2 .
  • 3rd layer green sensitive silver halide emulsion layer
  • the coating composition for the emulsion layer was prepared by mixing a green sensitive silver iodobromide emulsion (silver iodide: 6 mole percent) and a magenta coupler emulsion (containing 1-(2,4,6-trichlorophenyl)-3-[3-(2,6-di-t-amylphenoxyacetamido)benzamido]-5-pyrzaolone as a magenta coupler and tricresyl phosphate as a coupler solvent) in such a manner that the silver/coupler mole ratio became 9.5.
  • the coverage of silver 1.5 g/m 2 .
  • a filter layer composed of yellow colloid silver and gelatin.
  • the coating composition for the emulsion layer was prepared by mixing a blue sensitive silver iodibromide emulsion (silver iodide: 6 mole percent) and a yellow coupler emulsion (containing ⁇ -pivaloyl-2-chloro-5-[ ⁇ -(2,4-di-t-amylphenoxy)butanamido]acetanilide as a yellow coupler and dibutyl phthalate as a coupler solvent) in such a manner that the silver/coupler mole ratio became 8.0.
  • the coverage of silver 1.8 g/m 2 .
  • the 6th layer (protective layer):
  • the color reversal photographic film was exposed through an optical wedge to a tungsten lamp as a light source for 1/100 sec., and thereafter subjected to the following reversal processings:
  • compositions of the processing solutions used in the above processing steps were as follows:
  • Bleaching Time 1 min., 2 min., 2 min. 30 sec., 3 min., 3 min. 30 sec., 5 min., 10 min., 20 min.
  • each of the bleach solutions was allowed to stand for 5 days at 20° C. or for 4 days at 40° C. and then the residual percentage of hydrogen peroxide in the bleach solution was measured, the results being also shown in the same table.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Detergent Compositions (AREA)
US06/114,456 1979-01-23 1980-01-23 Photographic bleach solutions Expired - Lifetime US4301236A (en)

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JP54-6645 1979-01-23
JP664579A JPS5598750A (en) 1979-01-23 1979-01-23 Photographic bleaching composition

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US (1) US4301236A (en:Method)
JP (1) JPS5598750A (en:Method)
DE (1) DE3002375A1 (en:Method)
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GB (1) GB2042201B (en:Method)

Cited By (35)

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US4371609A (en) * 1980-07-19 1983-02-01 Konishiroku Photo Industry Co., Ltd. Forming method of a dye image
US4444873A (en) * 1981-12-29 1984-04-24 Fuji Photo Film Co., Ltd. Color photographic processing
US4454224A (en) * 1982-12-22 1984-06-12 Eastman Kodak Company Photographic bleaching compositions
US4524129A (en) * 1983-09-16 1985-06-18 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4529687A (en) * 1982-10-07 1985-07-16 Fuji Photo Film Co., Ltd. Method to form color image
US4717649A (en) * 1986-04-18 1988-01-05 Eastman Kodak Company Photographic bleach-fixing compositions
US4737450A (en) * 1986-04-18 1988-04-12 Eastman Kodak Company Method for bleach-fixing of photographic elements
US4923785A (en) * 1987-07-15 1990-05-08 Agfa Gevaert Ag Bleaching bath concentrate
US4939073A (en) * 1981-07-21 1990-07-03 Konishiroku Photo Industry Co., Ltd. Stablized method of light sensitive silver halide color photographic material
EP0428101A1 (en) * 1989-11-13 1991-05-22 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
WO1992007300A1 (en) * 1990-10-19 1992-04-30 Kodak Limited Photographic bleach solution
US5360700A (en) * 1989-01-13 1994-11-01 Konica Corporation Process for treating silver halide photographic light-sensitive material
US5362610A (en) * 1991-10-28 1994-11-08 Konica Corporation Photographic processing agent
EP0678783A1 (en) * 1994-04-20 1995-10-25 Eastman Kodak Company Hydrogen peroxide bleach composition for use with silver halide photographic elements
EP0679945A3 (en:Method) * 1994-04-20 1995-12-06 Eastman Kodak Co
US5541041A (en) * 1995-04-17 1996-07-30 Eastman Kodak Company Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements
US5547816A (en) * 1990-10-19 1996-08-20 Eastman Kodak Company Photographic processing method using bleach solution comprising hydrogen peroxide and halide ions
US5550009A (en) * 1995-04-17 1996-08-27 Eastman Kodak Company Stabilized peroxide bleaching solutions and their use for processing of photographic elements
EP0729065A1 (en) * 1995-02-21 1996-08-28 Eastman Kodak Company Peroxide composition and method for processing color silver halide photographic elements
US5554491A (en) * 1995-03-21 1996-09-10 Eastman Kodak Company Use of an alkaline prebath to activate an acidic peroxide bleach solution for processing color photographic elements
EP0747764A1 (en) * 1995-05-26 1996-12-11 Eastman Kodak Company Method of processing camera speed silver chloride photographic elements using peroxide bleaching solutions
US5614355A (en) * 1995-02-21 1997-03-25 Eastman Kodak Company Peroxide composition and method for processing color photographic elements containing predominantly chloride silver halide emulsions
US5629139A (en) * 1994-10-04 1997-05-13 Eastman Kodak Company Photographic processing solution composition
US5679501A (en) * 1992-04-24 1997-10-21 Fuji Photo Film Co., Ltd. Processing composition for silver halide photographic material and processing method using same
US5691118A (en) * 1996-10-10 1997-11-25 Eastman Kodak Company Color paper processing using two acidic stop solutions before and after bleaching
US5756270A (en) * 1995-09-29 1998-05-26 Eastman Kodak Company Method of processing a photographic silver halide color material
US5763147A (en) * 1995-02-21 1998-06-09 Eastman Kodak Company Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition
US5773202A (en) * 1995-02-21 1998-06-30 Haye; Shirleyanne Elizabeth Method for processing color photographic films using a peroxide bleaching composition
US5783376A (en) * 1994-04-20 1998-07-21 Eastman Kodak Company Sulfo-substituted carboxylates as buffers for photographic bleaches and bleach-fixes
US6040122A (en) * 1998-06-05 2000-03-21 Agfa Gevaert Nv Bleaching bath
US6136516A (en) * 1998-06-05 2000-10-24 Agfa-Gevaert N.V. Process for processing a photographic silver halide material
US6156488A (en) * 1990-07-26 2000-12-05 Eastman Kodak Company Photographic bleach compositions
US20030005945A1 (en) * 2000-03-13 2003-01-09 Hiroyuki Onishi Method for surface-treatment, surface-treated article and device for surface treatment
US6518002B1 (en) * 1997-02-06 2003-02-11 Eastman Kodak Company Photographic bleaching solution containing organic phosphorus acid anti-rust agent and method of use
US6703192B1 (en) 2003-02-28 2004-03-09 Eastman Kodak Company Photographic peracid bleaching composition, processing kit, and method of use

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DD222758A3 (de) * 1981-10-29 1985-05-22 Defa Zentralstelle Fuer Filmte Chinonhaltige loesung, insbesondere fotografisches bleichband
JPS62250450A (ja) * 1986-04-23 1987-10-31 Konika Corp ハロゲン化銀カラ−写真感光材料の処理方法
US5508151A (en) * 1994-12-22 1996-04-16 Eastman Kodak Company Processing of photographic elements using copper ligand complexes to catalyze peracid bleaching agents

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532634A (en) * 1966-03-01 1970-10-06 United States Borax Chem Bleaching compositions and methods
US3820997A (en) * 1971-10-15 1974-06-28 Fuji Photo Film Co Ltd Method of color development processing for forming stable photographic images
US3870520A (en) * 1972-10-05 1975-03-11 Fuji Photo Film Co Ltd Photographic processing composition
US4119557A (en) * 1975-12-18 1978-10-10 Lever Brothers Company Bleaching compositions and process for cleaning fabrics
US4203765A (en) * 1977-06-01 1980-05-20 Agfa-Gevaert N.V. Etch bleaching liquid with iron(III)ions

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728118A (en) * 1970-08-10 1973-04-17 Ibm Process for producing multiple recording in a single medium
JPS50109731A (en:Method) * 1974-02-05 1975-08-29
GB1473873A (en) * 1974-06-26 1977-05-18 Ciba Geigy Ag Photographic silver halide bleach-fix baths
JPS5165939A (ja) * 1974-12-05 1976-06-08 Fuji Photo Film Co Ltd Karaashashinzairyono shorihoho
JPS5249830A (en) * 1975-10-17 1977-04-21 Fuji Photo Film Co Ltd Photographic bleaching solution
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
JPS5811617B2 (ja) * 1976-08-18 1983-03-03 コニカ株式会社 ハロゲン化銀カラ−写真感光材料の処理方法
JPS59442B2 (ja) * 1977-02-18 1984-01-06 古河電気工業株式会社 安定化された過酸化水素溶液
JP3288625B2 (ja) * 1998-03-11 2002-06-04 株式会社日立製作所 インバータ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532634A (en) * 1966-03-01 1970-10-06 United States Borax Chem Bleaching compositions and methods
US3820997A (en) * 1971-10-15 1974-06-28 Fuji Photo Film Co Ltd Method of color development processing for forming stable photographic images
US3870520A (en) * 1972-10-05 1975-03-11 Fuji Photo Film Co Ltd Photographic processing composition
US4119557A (en) * 1975-12-18 1978-10-10 Lever Brothers Company Bleaching compositions and process for cleaning fabrics
US4203765A (en) * 1977-06-01 1980-05-20 Agfa-Gevaert N.V. Etch bleaching liquid with iron(III)ions

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371609A (en) * 1980-07-19 1983-02-01 Konishiroku Photo Industry Co., Ltd. Forming method of a dye image
US4939073A (en) * 1981-07-21 1990-07-03 Konishiroku Photo Industry Co., Ltd. Stablized method of light sensitive silver halide color photographic material
US4444873A (en) * 1981-12-29 1984-04-24 Fuji Photo Film Co., Ltd. Color photographic processing
US4529687A (en) * 1982-10-07 1985-07-16 Fuji Photo Film Co., Ltd. Method to form color image
US4454224A (en) * 1982-12-22 1984-06-12 Eastman Kodak Company Photographic bleaching compositions
US4524129A (en) * 1983-09-16 1985-06-18 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4717649A (en) * 1986-04-18 1988-01-05 Eastman Kodak Company Photographic bleach-fixing compositions
US4737450A (en) * 1986-04-18 1988-04-12 Eastman Kodak Company Method for bleach-fixing of photographic elements
US4923785A (en) * 1987-07-15 1990-05-08 Agfa Gevaert Ag Bleaching bath concentrate
US5360700A (en) * 1989-01-13 1994-11-01 Konica Corporation Process for treating silver halide photographic light-sensitive material
EP0428101A1 (en) * 1989-11-13 1991-05-22 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
US5607820A (en) * 1989-11-13 1997-03-04 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
US6156488A (en) * 1990-07-26 2000-12-05 Eastman Kodak Company Photographic bleach compositions
US5547816A (en) * 1990-10-19 1996-08-20 Eastman Kodak Company Photographic processing method using bleach solution comprising hydrogen peroxide and halide ions
WO1992007300A1 (en) * 1990-10-19 1992-04-30 Kodak Limited Photographic bleach solution
US5362610A (en) * 1991-10-28 1994-11-08 Konica Corporation Photographic processing agent
US5679501A (en) * 1992-04-24 1997-10-21 Fuji Photo Film Co., Ltd. Processing composition for silver halide photographic material and processing method using same
EP0678783A1 (en) * 1994-04-20 1995-10-25 Eastman Kodak Company Hydrogen peroxide bleach composition for use with silver halide photographic elements
EP0679945A3 (en:Method) * 1994-04-20 1995-12-06 Eastman Kodak Co
US5783376A (en) * 1994-04-20 1998-07-21 Eastman Kodak Company Sulfo-substituted carboxylates as buffers for photographic bleaches and bleach-fixes
US5641616A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Non-rehalogenating bleaching composition and its use to process silver halide photographic elements
US5641615A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Processing silver halide photographic elements with a non-rehalogenating peroxide bleaching composition
US5629139A (en) * 1994-10-04 1997-05-13 Eastman Kodak Company Photographic processing solution composition
US5763147A (en) * 1995-02-21 1998-06-09 Eastman Kodak Company Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition
US5614355A (en) * 1995-02-21 1997-03-25 Eastman Kodak Company Peroxide composition and method for processing color photographic elements containing predominantly chloride silver halide emulsions
EP0729065A1 (en) * 1995-02-21 1996-08-28 Eastman Kodak Company Peroxide composition and method for processing color silver halide photographic elements
US5773202A (en) * 1995-02-21 1998-06-30 Haye; Shirleyanne Elizabeth Method for processing color photographic films using a peroxide bleaching composition
EP0733946A1 (en) * 1995-03-21 1996-09-25 Eastman Kodak Company Use of an alkaline prebath to activate an acidic peroxide bleach solution for processing color photographic elements
US5554491A (en) * 1995-03-21 1996-09-10 Eastman Kodak Company Use of an alkaline prebath to activate an acidic peroxide bleach solution for processing color photographic elements
US5541041A (en) * 1995-04-17 1996-07-30 Eastman Kodak Company Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements
US5550009A (en) * 1995-04-17 1996-08-27 Eastman Kodak Company Stabilized peroxide bleaching solutions and their use for processing of photographic elements
EP0747764A1 (en) * 1995-05-26 1996-12-11 Eastman Kodak Company Method of processing camera speed silver chloride photographic elements using peroxide bleaching solutions
US5756270A (en) * 1995-09-29 1998-05-26 Eastman Kodak Company Method of processing a photographic silver halide color material
US5691118A (en) * 1996-10-10 1997-11-25 Eastman Kodak Company Color paper processing using two acidic stop solutions before and after bleaching
US6518002B1 (en) * 1997-02-06 2003-02-11 Eastman Kodak Company Photographic bleaching solution containing organic phosphorus acid anti-rust agent and method of use
US6136516A (en) * 1998-06-05 2000-10-24 Agfa-Gevaert N.V. Process for processing a photographic silver halide material
US6040122A (en) * 1998-06-05 2000-03-21 Agfa Gevaert Nv Bleaching bath
US20030005945A1 (en) * 2000-03-13 2003-01-09 Hiroyuki Onishi Method for surface-treatment, surface-treated article and device for surface treatment
US7169444B2 (en) * 2000-03-13 2007-01-30 Seiko Epson Corporation Method for treating surface of ink jet recording medium having recorded image
US6703192B1 (en) 2003-02-28 2004-03-09 Eastman Kodak Company Photographic peracid bleaching composition, processing kit, and method of use
US20040171506A1 (en) * 2003-02-28 2004-09-02 Haye Shirleyanne E. Photographic peracid bleaching composition, processing kit, and method of use
US6852477B2 (en) 2003-02-28 2005-02-08 Eastman Kodak Company Photographic peracid bleaching composition, processing kit, and method of use

Also Published As

Publication number Publication date
FR2447570B1 (fr) 1987-08-14
FR2447570A1 (fr) 1980-08-22
GB2042201B (en) 1983-01-26
DE3002375A1 (de) 1980-07-31
GB2042201A (en) 1980-09-17
JPS6116067B2 (en:Method) 1986-04-28
JPS5598750A (en) 1980-07-28
DE3002375C2 (en:Method) 1987-08-27

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